CN1285502C - Method for producing self-supporting activated carbon structures - Google Patents

Abstract

A method for producing self-supporting activated carbon structures is disclosed. The method comprises the steps of mixing a granular activated carbon, a binder material, a carbonization agent, and a liquid to produce a semi-plastic mixture; compacting the mixture using compacting pressures of or greater than about 100 pounds per square inch to form a three-dimensional structure; and heating the structure to an elevated temperature of or greater than about 300 DEG C to produce a self-supporting activated carbon structure. The granular activated carbon is of any particle size between approximately 4 and 325 mesh U.S. Sieve Series, and the binder is a ground cereal grain, cereal rain flour or a tuber flour. The resultant structure may then be cooled to near-ambient temperatures under an essentially inert atmosphere. Such structures can exhibit good mechanical strengths, adsorption capacities nearly equivalent to those of the activated carbon used in their preparation, and appreciable electrical conductivity. Such structures can also exhibit the chemical inertness, very high temperature tolerance (>1000 DEG C) in non-oxidizing environments, and the elevated temperature tolerance in mildly oxidizing environments typically associated with activated carbons.

Description

The method of production self-supporting activation carbon structure body

The field of the invention

The present invention relates to production self-supporting activation carbon structure body method and, more particularly, relate to the method for using starting raw material cheap, that obtain easily such as kryptol production self-supporting activation carbon structure body.

Background of the present invention

Self-supporting activation carbon structure body has the purposes of height.For example, self-supporting activation carbon structure body has been used as filtering medium, support of the catalyst, sorbent material, and electrode.In some applications, the electroconductibility of activation carbon structure body is that regeneration or electrochemistry purpose are needed.The shape of activation carbon structure body or form are through selecting to meet predetermined purposes requirement.These shapes or form comprise cylindrical, rectangle or square block, honeycomb, plate, thin slice and various other three dimensional form.

The currently known methods of producing activation carbon structure body generally is classified as three groups: organic materials is shaped and activation; Be coated with backing material with the activation charcoal; Maybe will activate the charcoal particle mixes with binding agent to form the structure of desired shape.

In first group, by selected organic materials is configured as a kind of structure, the structure of this shaping is carbonized and activates after this, forms self-supporting activation carbon structure body.Generally, these organic materialss are the solids or the semi-solid things that can produce a large amount of carbonaceous coke when carbonization.Therefore it is synthetic that this type of material tends to, as thermosetting resin be relatively costly, when comparing with the natural matter of the activation charcoal that is used to produce the microgranular and pulverizing of commodity.Limited amount activation charcoal particle can be added to the absorption property (i.e. " activity ") of organic materials to improve formed structure before being shaped.Various other fillers also can be added to before being shaped in the organic materials so that provide additional strength or porosity for formed structure.

The shaping of structure can be by for example compacting, molding, or extrude and carry out.This carbonization and activation can be implemented by method well known in the prior art.Can be contemplated that, the carbonization of this type of structure and activation must be formed the cracking of structure and be guaranteed the uniform activity of formation in the entire structure body (that is, adsorbing void content or loading capacity) carrying out under the speed (being the slow variation of low temperature or temperature) more slowly to prevent.Process rate slowly because the slow heating of this structure or slowly activation, spend inherently higher because need the long stove residence time.The long stove residence time causes the high product cost inherently.Even use speed slowly; be very difficult to predictably be created in the whole carbon structure and uniform activity arranged (promptly; absorption void content or loading capacity) structure extremely be difficult to be enough to provide other to set up and/or keep under temperature of active rate very slowly because run through the necessary uniform heat transfer of entire structure body and mass transfer.Simultaneously, the performance of formed activation charcoal be limited to produce from initial organic materials those and be limited to the improvement degree of giving by the interpolation of activation charcoal particle or other filler.The economy of being produced activation carbon structure body by this method is very disadvantageous, even the electroconductibility of these structures will be the potential height.

In second group, activation carbon structure body is to form from non-carbon material substrate, and it is subsequently with the coating of activation charcoal.Typically, the activation carbon coating is applied on the entire structure body, comprising the structure internal surface that defines than macrovoid and void volume.The approach of several types has been used to obtain required activation carbon coating.

In a kind of approach, binding agent/activation charcoal mixt can be coated on the surface of body support structure.Useful binding agent is to adhere to simultaneously on support material and the activation charcoal those well.For example, thermoplastic resin and hotmelt can be used in the activation carbon coating is fixed on the support material.Yet, should select binding agent carefully, so that binding agent is not filled activation charcoal absorption pore space or prevented to enter it.Additionally, in another approach, the organic materials that can produce a large amount of carbonaceous coke when pyrolysis can be coated on the surface of structure.After this coating, this organic materials is carbonized and activates.General this approach of hope use forms on the surface of structure evenly, the successive carbon-coating.This carbon-coating has been found that can provide good electrical conductivity and structural integrity.In another approach, the organic materials of last approach has the very activation or the blending mutually of non-activated carbon granule of small grain size with the typical case.Top coat is carbonization and activation then.For whole three approach, coating generally be applied on the body support structure that can tolerate selected processing condition and coating material on, and not significant degraded.Typically, this body support structure is a pottery.

Though these approach can form the uniform carbon coating with excellent activity and purposes, the quality of this structure and volume base loading capacity are limited.That is to say that the activation charcoal is to exist as just top coat and do not require loading capacity for beneath support material.Therefore, the quality of this structure and volume base loading capacity all are subjected to the restriction of support material, for structure has increased sizable volume and quality, but not corresponding raising on the structure activity.And thermosetting resin, or the precursor of this resin are favourable organic coating materials.This resinoid can have toxicity and/or the economic problems relevant with their use, and these make their application become difficult and/or expensive.In addition, the performance range of the activation charcoal that forms from these materials is limited, because this type of performance is main relevant with starting raw material.Simultaneously, the essential activation of these materials is typically being carried out under the condition as mild as a dove best to guarantee the even activation in the entire structure body.That is to say, need gentle activation condition to prevent from the outside surface of structure, highly to activate the formation of charcoal,, if any, activate on the carbon of the inside of structure marginality ground only then.The use of this type of mild conditions has increased the activation furnace residence time, the production cost that has reduced productivity and caused significantly improving.

In addition, the support material of structure that is used to prepare second group activation charcoal coating generally is not an electroconductibility.Therefore, any electroconductibility relevant with these structures depends on the electroconductibility of carbon coating.Obviously, high conductivity if desired must be noted that then this coating provides the contact of successive carbon on whole its surface coverage.

In the 3rd group, activation carbon structure body is that the use by binding agent will activate the charcoal particle bond and become required shape to produce.The method of this group provides the intrinsic advantage of comparing with the method for being instructed in two groups of the fronts, comprising significantly improved production economy, the wider spendable and activation carbon activity that can realize, the structural loading capacity of bigger volumetrical, more macrostructure body quality-base loading capacity and, sometimes, improved structure electroconductibility.

Generally, this method adopts powdery activation charcoal, but fibrous activation charcoal also uses.Once in a while, very little order number (that is, being lower than about 80 order U.S. sieve series granularities) carbon is formed structure.There is situation seldom promptly also to form activation carbon structure body than the activation charcoal of big mesh size.This carbon granule forms the hard structure body by using in many dissimilar binding agents one or more.Employed actual adhesive method depends on selected nature of binder.

For example, thermoplastic adhesive can heat or solvent softening and become tackiness agent.In this way, adjacent carbon granule is bondd by these thermoplastic binder, make form and solvent remove or cool off after keep required structure.For the situation of binding agent such as clay or ceramic precursor, water typically is used as solvent so that plastics combine with the activation charcoal.After formation and drying, this carbon granule is retained in the matrix of binding agent.For two types binding agent, this structure is by using such as extruding, molding, and the technology that compacting waits and so on forms.Uncommon is before forming all ingredients to be added in activation charcoal-binder blend to improve the plasticity of mixture, and this helps the formation of desired structure body.

Thermosetting resin is also as binding agent.These binding agents mix with activation charcoal particle, form required structure, and cured resin.Sometimes other binding agent and this thermosetting resin coupling.

Other binding agent that has been used to form activation carbon structure body comprises Resins, epoxy, polyvinyl alcohol, and starch, chemically-modified cellulose, monose, disaccharides, polysaccharide, various fluoropolymers, or the like, combine individually or with other binding agent.Usually, these and other binding agent is used in combination with the liquid phase with solvation performance, so that form the plasticity can be processed into desired structure easily or semi plastic, mouldable material.Although used various binding agents, also do not know to use at present grain, cereals meal or the stem tuber powder of grinding.After formation, this liquid is removed from structure, structure hardening at this moment.

In order to use these binding agents effectively, must be noted that the loading capacity (that is carbon " activity ") of institute's agglutinating activation charcoal does not have bonded dose to reduce significantly.Cause minimizing owing to activation charcoal particulate is too much adhesive coated.This is the adhesive coated charcoal of sealing activation effectively particulate surface too much, therefore owing to carrying restriction that absorption can not be taken place.The absorption that binding agent is activated charcoal also can cause the activity that lowers.For example, for solvent remollescent binding agent, some binding agents of use solubilized of excessive solvent.The binding agent of solvation is activated charcoal and absorbs, and reduces its loading capacity.This capacity reduces estimates it is a specific question, when high-adsorption-capacity activation charcoal is bonded.

It is also important that binding agent does not increase the quality or the volume of activation carbon structure widely.Typically, the ratio of binding agent is big more in structure, and the physical strength of structure is big more.Unfortunately, can belong to the structure volume of this binding agent and the ratio of quality will improve along with increasing the binding agent consumption.This raising reduces the apparent mass or the volume base loading capacity of structure significantly by the contribution of diluting the activation charcoal effectively.Excessively binding agent uses the internal pore volume that also can reduce the activation carbon structure significantly.This so cause structure shown to the mobile high-drag or the difference kinetics of adsorption.

Typically, the suitability of the activation carbon structure of these types is subjected to the performance limitations of binding agent.For example, adopt the activation carbon structure of solvent remollescent binding agent can not be softening or dissolve use in the presence of the solvent of this binding agent again.Similarly, adopting the structure of thermoplastic adhesive or not to be higher than under the temperature of this softening temperature at the softening temperature of binding agent uses.Cured thermosetting can alleviate this class problem in some aspects.Unfortunately, the resin of these types is expensive inherently, has the toxicity problem relevant with them, or is in the physical form that is difficult to use the absorption that maybe can cause binding agent and follow-up activation carbon activity loss.In addition, use the electroconductibility of the structure that the binding agent of these types produces to estimate it is low-down, owing to the limited contact between the carbon granule in this structure with owing to the insulating property of selected binding agent.

These types to be restricted to called optical imaging and various technology open, attempt to widen by using the suitability of the activation carbon structure that this type of binding agent produces.For example, in some instructions, formed activation carbon structure is accepted high temperature with further sclerosis or solidify this binding agent or partially or even wholly carbonization or this binding agent of calcination.But the processing expectation such as carbonization and especially calcining of the binding agent of carbonization improves the electroconductibility of handled activation carbon structure body basically.

This type of thermal treatment can make more anti-all kinds of SOLVENTS of formed activation carbon structure and/or pyritous influence.Yet typically, thermal treatment such as carbonization or calcining can partly be volatilized this binding agent and be caused reducing physical strength.If calcining under the needed high temperature of bigger electroconductibility in order to obtain, then this is real especially.This loss of intensity can be by the binding agent that in structure, uses the increase of amount compensate.But the use meeting of the binding agent of additional content correspondingly improves the use cost related with selected binding agent, and makes formed structure become very expensive.In addition, the use of the binding agent of additional content also can reduce the quality and the volume activity of formed structure.Simultaneously, some binding agents as some thermosetting resins, typically do not form porous coke.Therefore, the increase of the binding agent of these types is used, even when carbonization or calcination, can seriously be limited in the transmission in the activation carbon structure.

As if show, if activation charcoal particulate adhesive-free mode agglutinating appropriate method can determine that then typically relevant with the use of the binding agent that is used to form activation carbon structure difficulty can be avoided.Because the chemical property of activation charcoal, the bonding expectation of this adhesive-free mode is very difficult, if not impossible words.Yet some instructions have report in the literature, and the use that they have been described by special sintering technology forms structure from activation charcoal particle.The use of this type of instruction is not determined, still can estimate reasonably that the energy requirement of this type of technology is sizable, makes its practice not allow economically.

For this specification sheets, some term has the following meaning for the hot-work of carbon-based material." carbonization " is meant that the carbon containing organic materials changes into the higher carbon content material, is commonly referred to coke.Carbonization usually is exposed to high temperature by organic materials, typically carries out in relative inertness or mild oxidation atmosphere.This exposure is used for removing at organic materials contained a high proportion of heteroatoms such as oxygen, hydrogen, nitrogen, and sulphur.This type of heteroatoms typically is removed as volatile gases, and these gases are usually by such as water, carbon monoxide, and carbonic acid gas, the compound of oxynitride and volatile sulfur compound and so on is formed.The chemical coagulation process that nonvolatile carbon species forms coke will take place with removing simultaneously of this volatile materials.Carbonization temperature is typically greater than 100 ℃ and be lower than 500 ℃.Though typically, carbonization is finished under about 500 to 600 ℃ temperature basically,, if coke temperature is brought up to higher value, then the volatile materials of additional content can come out from coke.

" calcining " is meant that material is exposed to high temperature.These high temperature are assumed that usually greater than about 600 or 700 ℃ but can hang down.For oxidizable material, as carbon, calcining is implemented under inert atmosphere usually.The carbonization of material must side by side take place before calcining or with calcining.For example, consideration is placed on the not carbonization organic materials in 800 ℃ of stoves of operating down.Along with this material is heated to 800 ℃, it is with regard to carbonization.After reaching 800 ℃ temperature, at this temperature lower calcination.The carbonization that carbonization therein and calcining are implemented with material as processing step basically is in this processing step institute this type of situation of inherent, and this term calcining can be used to this overall operation (collective operation).This term pyrolysis also can be applicable to the overall operation of this type.In the initial calcination process of the material of carbonization, the chemical coagulation that limited amount volatile matter can come out and the increase of nonvolatile carbon species can take place as gas.This type of generation meeting improves along with calcining temperature and proceeds, and is considered to irreversible basically and completely.That is to say, discharge or chemical coagulation any significant the adding can not cause volatile matter to the follow-up calcining under the fixed temperature of the carbon that this temperature lower calcination is crossed in advance.Be noted that the not only carbonization of given material, and can be calcined repeatedly as required.

" activation " means being typically greater than that carbon is exposed to oxidizing gas such as water vapor or carbonic acid gas under about 700 ℃ temperature, so that make the part gasification of carbon selectively.For the activation charcoal of microgranular and many other types, this optionally gasifies and typically takes place with its inside on the surface of each carbon particulate simultaneously.This type of optionally gasification can cause adsorbing the hole volumetrical and increase.This absorption void content and its sizes related usually are called " activity ".This type of of significant quantity " activity " be the activation charcoal clear and definite characteristic.

Can infer the method for the production self-supporting activation carbon structure body (especially from granular carbon) that also openly is not entirely satisfactory from the front.Therefore, target of the present invention provides improving one's methods of production self-supporting activation carbon structure body, by starting raw material relatively cheap, that obtain easily use and the short production time provides advantage on cost and the performance.Target of the present invention is with cheap granular carbon and novel, nontoxic binding agent and the coupling of carbonization reagent with low toxicity.Another target of the present invention is that carbonization reagent has been emphasized the use of selected binding agent.Also have a target of the present invention to provide a kind of method, it does not need the activating process step, has therefore reduced the cost burden for some prior aries ran into.

In addition, target of the present invention provides activation carbon structure body, and it has the tamped density of even carbon activity and bonding activation carbon particle, the latter near or equal the not tamped density of agglutinating granular carbon.Another target of the present invention provides self-supporting activation carbon structure body, it can withstand to be exposed in non-oxidizable environment and be higher than 300 ℃ temperature, have with the relevant unreactiveness of activation charcoal with it and have electroconductibility, this electroconductibility near or surpass the electroconductibility of the packed bed of employed granular carbon in its preparation.Additional objects and advantages will become clearer from narration of the present invention.

The present invention's general introduction

Generally, the present invention includes by using the method for granular carbon production self-supporting activation carbon structure body (also being called " SSACS " here).This method comprises (a) mangcorn shaped activated carbon, binder material, and carbonization reagent and liquid are to produce the semi plastic mixture; (b) come this mixture of compacting to form three-dimensional structure by using approximately or greater than about 100 pounds/square inch compaction pressure; (c) in inert atmosphere basically this structure of heating to greater than or about 300 ℃ high temperature, produce SSACS.Randomly, this structure is dried before the heating after compacting and at high temperature.After heating, preferably in the inert atmosphere SSACS is being cooled to be lower than about 300 ℃ basically.

In first step, this granular carbon preferably has and passes about 4 mesh sieve and be retained in granularity on about 325 mesh sieve, according to U.S. sieve series (Sieve Series), and ASTM specification (Specification) E-11-61.This type of is measured and also is typically expressed as 4 * 325 sieve meshes.Can expect, microgranular non-activated carbon, coke and graphite also can be used in the enforcement of the present invention.Instruction of the present invention also estimates to be applicable to selectively fiber, granulation and carbon that pulverize, coke, and graphite.

This binder material comprises the cereal-granules of grinding, cereal-granules powder or stem tuber flour; Or their mixture.Additionally, polysaccharide, as chitin, various natural gum, or chemically-modified cellulose can be potential as binding agent.Preferably, this binding agent comprises cereal-granules powder or stem tuber powder.More preferably, this binding agent is wheat-flour or potato powder.Binding agent is greater than 1 part of binding agent with the quality-base ratio of activation charcoal, with respect to 5 parts of charcoals.In preferred embodiments, use the ratio of 3-4 part binding agent with respect to 5 parts of activation charcoals.This carbonization reagent comprises any reagent of the productive rate (amount) of the carbon that raising obtains from the carbonaceous material that carries out carbonization, does not comprise zinc chloride.Preferred carbonization reagent be show hypotoxic those and comprise ammonium chloride and diammonium hydrogen phosphate.The mixture of two or more carbonization reagent can use.

The liquid of significant quantity is used for wetting carbon and binder material simultaneously.Preferably, also softening this binding agent of this liquid.In preferred embodiments, this liquid also can this carbonization reagent of solvation.More preferably, carbonization reagent be dissolved in this liquid before activation charcoal and binding agent mix.Suitable liquid not should with carbon, binding agent or carbonization reagent react and should have certain volatility make it can be from the activation carbon structure body that wet method forms evaporation but can not decompose.Water is preferred liquid.

In second step, mixture by use greater than or about 100 pounds/square inch pressure come compacting, have the configuration of required three-dimensional structure with formation.In another embodiment, this structure is dry after compacting.In third step, structure is being heated to high temperature to produce SSACS in the inert atmosphere basically.High temperature be greater than or about 300 ℃.Preferably, this high temperature is greater than about 500 ℃; Most preferably, this temperature is greater than about 900 ℃.In the 4th optional step, this structure is being cooled to below about 300 ℃ in the inert atmosphere basically.

Formed self-supporting activation carbon structure body can be with any 3D shape production basically.These structures can be heat and chemically stable and uniform; With the demonstration good mechanical strength, bigger electroconductibility, the loading capacity of the loading capacity of the activation charcoal that in their preparation, uses no better than and near or the bonding that equals the tamped density of agglutinating granular activated charcoal not (they constitute from this activation charcoal) activate the charcoal tamped density.For example, the activation charcoal in these structures can keep it initial not agglutinating loading capacity nearly 90% or higher loading capacity.If be heated to sufficiently high temperature in preparation process, then this type of structure also can demonstrate than the shown more excellent electroconductibility of electroconductibility that goes out of the packed bed of employed not agglutinating granular activated charcoal in the preparation of self-supporting activation carbon structure body.This type of structure also shows unreactiveness, and very high temperature tolerance (＞1000 ℃) in non-oxidizable environment is with the high temperature tolerance limit in typically relevant with activation charcoal mild oxidation environment.

Because the SSACS that use of the present invention is produced can have any form, include but not limited to cylindrical, square or rectangular block, honeycomb, plate, thin slice and various other three dimensional form.These various forms of potential restrictions are comprised minimal structure thickness, and it should equal or exceed the highest diameter of granular carbon particulate that uses in the preparation of SSACS.SSACS can prove and can be used in the various application, as is used for from gas, removes the sorbent material and/or the filtering medium of pollutent or other material in steam or the liquid.These self-supporting activation carbon structure bodies make them demonstrate sizable electroconductibility after preparation.Therefore, these structures can be used as resistance heater, as electric reproducibility absorption agent, or as the electrode that in electrochemical treatment and/or application, uses.This type of electrochemical treatment and/or application can include, but not limited to battery, electrical condenser, electrochemistry metal recovery/remove, electron ionization effect, and electrosynthesis.

Further feature of the present invention, aspect and advantage will describe in detail below of the present invention and reading in detail of claims and become better understood or clearer.

Detailed description of the present invention

In one embodiment of the invention, the production method of SSACS comprises that (a) mixes the granular activated charcoal, binder material, and carbonization reagent, and liquid, production has basically the semi plastic mixture of denseness uniformly; (b) come this mixture of compacting by using approximately or, to form three-dimensional structure greater than about 100 pounds/square inch compaction pressure; (c) in inert atmosphere basically this structure of heating to greater than or about 300 ℃ high temperature to produce SSACS.Randomly, this structure is dried after compacting and before being exposed to high temperature.Optional, also have cooling step (d) after this heating steps, wherein self-supporting activation carbon structure body is being cooled to below about 300 ℃ in the inert atmosphere basically.

In first step of embodiment of the present invention, granular activated charcoal and binder material make the material blend contain greater than about 1 part of binding agent/per five parts of activation charcoals with certain amount blending.Preferably, the binding agent for every 3-4 part uses 5 parts of charcoals.The addition of liquid be enough to simultaneously wetting this carbon and binding agent and, preferred, also softening this binding agent.Carbonization reagent is added in the mixture then.More preferably, carbonization reagent had been dissolved in this liquid before liquid being joined in carbon and the binding agent.Liquid, carbonization reagent, carbon and binding agent mix, till having obtained to have the semi-plastic material of minimally of even denseness.

In second step, this semi plastic material is produced required node configuration by using known molding, extruding or other forming technique is compacted.Preferably, after compacting, the material that wet method forms carries out drying.In third step, formed material is heated, and preferably in inert atmosphere, arrives more than or equal to about 300 ℃ temperature.Formed activation charcoal self-supporting structure is cooled in inert atmosphere basically subsequently and is lower than about 300 ℃.

Useful granular activated charcoal is that common commercially available granular activated charcoal also can be from for example coal, timber, Exocarpium cocois (Cocos nucifera L), other hard shell, fruit nuclear or the Nux Canarii albi formation of any suitable starting raw material.This granular activated charcoal preferably has the granularity between about 4 orders and about 325 orders.Generally, can't use greater than 3 purpose particle sizes.On average be lower than about 325 purpose particle sizes and generally be classified as powdered carbon.

In a preferred embodiment of the invention, this granular activated charcoal has and is lower than 10 orders and greater than 325 purpose mean particle sizes.For example, have the nominal mesh size, as 10 * 20,12 * 20,12 * 40,40 * 80,80 * 325, or 10 * 325 purposes activation charcoal all can use.Activation charcoal with 4 * 40 purpose particle sizes is preferred, if mean particle size is lower than about 10 orders.The activation charcoal that has greater than the mean particle size of 10 orders (being the 4-10 order) can both use, though can improve mechanical property and the outward appearance of the SSACS that forms if the carbon of these bigger order numbers and less order number (being the 10-325 order) granular activated charcoal coupling is used.For physical strength and the outward appearance of formed SSACS, littler mean mesh size is preferred.

Some powdered activation charcoals can be used by the present invention, but can have some difficulties.For example, formed SSACS is dry or ftracture when being heated to high temperature.If one or more in the size of formed SSACS (dimensions) are to minimize, then this cracking can be avoided in some cases.Therefore, thin slice, pellet, ball etc. are sometimes by using this method to prepare from powdered carbon.Can estimate that also fiber and/or granulous activation charcoal also can use.Yet the expensive use that stops them probably that the typical case is relevant with the activation charcoal of this type of form is in order to help this granular activated charcoal.Can estimate that also microgranular non-activated carbon, coke and graphite can be used for producing SSACS by method of the present invention.

Spendable in the present invention granular activated charcoal can demonstrate any available loading capacity (i.e. " activity ").Having high or extremely SA granular activated charcoal can be used in by this method production self-supporting structure.Method of the present invention should make the activity of activation charcoal obtain significantly keeping, even after in being incorporated into SSACS.In addition, in case form and thermal treatment, can expect that this activation carbon structure body can further activate by use well-known program and condition in correlative technology field.Yet, in order to recover or to improve the loading capacity of the activation charcoal of being introduced and the further activation carried out does not need or even do not desire because typically expense big with time-consuming.This further activation also can reduce the physical integrity that binding agent derives from coke, therefore weakens SSACS.Therefore, preferably use the granular activated charcoal in the present invention, it demonstrates enough activity, so that formed SSACS shows the loading capacity of being desireed, but depends on further activation.

These granular activated charcoals can show any available density.Density for being suitable for the granular activated charcoal among the present invention does not have preferential scope or restriction.Yet be noted that the physical strength and the electroconductibility that have typically shown the reduction level than low density carbon.These reduction levels in the granular activated charcoal can cause the reduction of the correlated performance of formed SSACS.

Binder material comprises the grain of grinding, cereals meal and stem tuber powder.Preferred this material is pulverized, be commonly referred to " powder " and known be relatively cheap.In one embodiment of the invention, pruinescence finds to produce self-supporting activation carbon structure body, and it is better than with having those that the grinding binding agent of volume particle size more produced.Grain includes, but not limited to wheat, corn, rye, oat, rice, and barley.Stem tuber powder comprises potato powder.Preferably, this binding agent is wheat-flour or potato powder.Several these materials demonstrate the limited swelling or the tendency of foaming in carbonization process.This swelling or foaming can be used for suppressing or eliminating by the making of carbonization reagent of appropriate amount.Because as food, they any important toxicity problem should not occur as the use of binding agent to the material of these types usually.

Although can use the binding agent of various other types, it is useful to estimate that they do not resemble the binder material disclosed herein, because they can cause higher cost, the toxicity problem occurs and/or lacks by the wetting ability of selected liquid.The binding agent of these other types can comprise those materials that generally are classified as polysaccharide or chemical modification polysaccharide.Example includes, but not limited to chitin, various natural gum, methylcellulose gum, or carboxymethyl cellulose.Any binding agent should be able to be wetting and form mixture and demonstrate limited solubleness in the moistening selected liquid for carbon and binding agent by selected liquid.Limited solubleness is useful because this binding agent localization rest on the surface of granular activated charcoal.Therefore, binding agent penetrates into the sealing or the filling that stop basically in the carbon granules and activate the charcoal adsorption site and is inhibited.In addition, when being exposed to high temperature in the presence of selected carbonization reagent, spendable binding agent should be seldom or is not shown swelling.Have been found that the polysaccharide that is often referred to starch is the improper binding agent of enforcement of the present invention, because excessive swelling trend.

The liquid that is used for the preferred embodiments of the invention is wetting this carbon simultaneously, and wetting and softening this binding agent.This " wetting liquid " not with this carbon, binding agent or carbonization reagent react and volatility more or less, make it can be from the activation carbon structure body that wet method forms evaporation but the decomposition of any kind does not take place.It is desirable to, wetting liquid can make selected carbonization reagent solvation with certain amount, makes wetting liquid can be used as vehicle, and carbonization reagent is evenly distributed in activation charcoal-binder mixtures.This wetting liquid-carbonization reagent solution can be called " Wetting Solution ".Wish in addition this wetting liquid be cheap with have seldom or do not have toxicity problem or other safety problem relevant with its use.Preferably, this wetting liquid is a water.

This carbonization reagent comprises any reagent of the productive rate of the carbon that raising obtains from the carbonaceous material that carries out carbonization, does not comprise zinc chloride.Preferably, the present invention uses and demonstrates hypotoxic carbonization reagent such as ammonium chloride and diammonium hydrogen phosphate.The novel use of this type of carbonization reagent makes coke yield and the intensity of the SSACS that obtains from the binding agent of specified rate that increase be arranged in enforcement of the present invention, but the coke volume obviously improves without any corresponding.Therefore, the amount of coke binding agent and efficient can improve in SSACS, but do not have the requisite increase by the binding agent volume that other method well known in the prior art ran into.In addition, this raising also provides overactivity charcoal density.In addition, from carbonization reagent the formed porous binding agent of the effect of binder material coke has been protected the path of the adsorption site of the activation charcoal that enters SSACS.This result is opposite with prior art, and the SSACS binder content of Zeng Jiaing can seriously suppress absorbate and delivers into this activation charcoal in the prior art.

Generally, carbonization reagent is used for improving the productive rate of the carbon that obtains from the carbonaceous material that carries out carbonization of the preparation that is used to activate charcoal.Also have some evidences to show, the performance of the coke of being produced by the use of carbonization reagent is different from does not use those that these reagent place obtain.Usually, carbonization reagent is applied in highly oxidized carbonaceous material such as grizzle, Mierocrystalline cellulose, and sugar and polysaccharide material are to improve the coke productive rate.Specific method utilizes these their these carbonization reagent to be used to improve the carbonization productive rate, does not determine.This type of reagent can strengthen chemical dehydration or reduce the carbonization temperature of carbonaceous material (they put on this material).Simultaneously, some reagent can promote molecule crosslinked in carbonization process significantly and introduce the anionicsite of this reagent and even cause forming and have the coke that improves intensity.This type of crosslinked carbonization reagent comprises for example phosphoric acid, the ammonium salt of phosphoric acid, and boric acid.Noncrosslinking reagent comprises anhydrous hydrogen chloride, anhydrous hydrogen bromide, anhydrous hydrogen iodide, ammonium chloride, brometo de amonio, ammonium iodide, sulfuric acid, sulphur trioxide, and ammonium sulfate.These carbonization reagent can separately or be united use.

Can expect, any on-gaseous carbonization reagent, but except the zinc chloride, can be used in the enforcement of the present invention.Yet, many these carbonization reagent be heavy corrosion or have relevant with their use outstanding safety or toxicity problem in addition.Simultaneously, some reagent can be incorporated into residue in the formed carbon, and this has influenced its use in some applications.Target of the present invention provides a kind of method, and it has the toxicity problem of the minimum relevant with it.Therefore, the ammonium salt that the preferred carbonization reagent that is used for the present invention is phosphoric acid, ammonium chloride, brometo de amonio, ammonium iodide, and ammonium sulfate.Phosphoric acid does not have the aggressiveness of corrosion property, does not have the outstanding toxicity problem that some reagent place of listing in the paragraph in front run into yet.Therefore, phosphoric acid in the solution of phase dilution, is preferred carbonization reagent in the present invention.Gaseous state carbonization reagent also estimates to assist the carbonization of the binding agent that uses in the present invention, but is difficult to use, because need do extensively to improve to this method.Therefore, the use of gaseous state carbonization reagent is not recommended.

The ammonium salt of phosphoric acid and phosphoric acid can cause the improvement of the intensity of SSACS as the use of carbonization reagent, compares with other carbonization reagent.Yet phosphate anion reagent can stay the phosphoric acid salt residue in formed SSACS.For some application, this type of residue should be removed by washing, before the use of SSACS.On the other hand, can expect that the ammonium halide salts can not brought relatively large residue into as product S SACS as using of carbonization reagent.With various safety, toxicity, efficient and economic factors are the basis, and ammonium chloride is the most preferred carbonization reagent of SSACS, and this SSACS must have minimum carbonization reagent and derive from pollution.Although this type of pollution problem is too big stake not, diammonium hydrogen phosphate is by preferred carbonization reagent.Under any circumstance, the invention provides the use of any amount of carbonization reagent, make and farthest to reduce for the problem for the carbonization agent residues among the final SSACS.

In practice, the granular activated charcoal, wetting liquid, carbonization reagent and binding agent mix, till having obtained to have uniform semi-plastic material.Semi-plastic material is meant that mixture has some cohesions and deformed by institute's applied pressure, keeps this cohesion simultaneously.Do not wish that generally this mixture is perfectly plastic and is deformed into Any shape by minimal pressure easily.Perfectly plastic mixture can use, but is difficult to keep required structural shape before drying and/or carbonization/calcining.Component is mixed and can be finished by use known any methods involving in association area, yet following method is preferred.

In a preferred embodiment of the invention, at first, this carbonization reagent is dissolved in and forms Wetting Solution in the wetting liquid.This wetting liquid preferably water and the concentration of carbonization reagent in Wetting Solution typically in 10 (wt) % scope.Higher and carbonization reagent lower concentration can use.The optimum quantity of carbonization reagent depends on the desired properties of the SSACS that forms and the volume of the Wetting Solution that absorbs by the amount of the binding agent that uses in mixture and by the granular activated charcoal is determined.This optimum quantity can be determined by the preparation of SSACS the most easily by the carbonization reagent that uses different concns in Wetting Solution and those concentration of passing through to determine to optimize desirable SSACS characteristic.The use of Wetting Solution, rather than each ground of wetting liquid and carbonization reagent added in this carbon, the more uniform distribution of carbonization reagent generally caused.This is uniform distribution and then caused forming the SSACS with more even composition and performance more.

In case preparation, this moistening solution and the blending of granular activated charcoal.The consumption of Wetting Solution depends on porosity and moistening speed that activates charcoal and the amount that is added to the binding agent in the mixture subsequently.If desired, Wetting Solution-carbon blend can mix, and is wetting equably to guarantee the wetted solution of whole carbon granules.In this stage of this method, usually observe more a spot of unconjugated Wetting Solution.Then, this binder material is added in Wetting Solution-granular activated charcoal mixt.People observe, and this binding agent adheres to the surface of carbon granules at once.This blend mixes, and scribbles binding agent equably until each carbon granules and is evenly dispersed in the whole carbon with this binding agent.The blending means of known any kind can be used in correlation technique, as long as this blending means does not seriously influence granular activated charcoal particulate quality.Mixing time is several minutes or still less typically.At this moment, mixture should tend to caking and be semi-plastic.The carbon granules of coating can present moisture state.For the bonded Wetting Solution should not be transparent.

For most granular activated charcoal, can use the binding agent of 2-5 part (weight) for per 5 parts granular activated charcoal.Be lower than about 2 parts binder amount and generally cause forming the SSACS that lacks enough mechanical integrities.Can use greater than 5 parts binder amount, but should amount normally too high and only improve slightly, if any, the SSACS performance.Typically, acceptable SSACS characteristic obtains by the binding agent that uses 3-4 part usually.Overactivity charcoal density in formed SSACS and from the minimum SSACS shrinking percentage that the carbonization/calcining of binding agent causes obtains when the amount when binding agent minimizes.

Though various other combination processes can be used, this blending means is considered to have some advantage.For example, dry binder applying on wetting granular activated charcoal easily provides adhesive coated relatively uniformly on each carbon granules.In addition, think that meeting suppresses to be activated from binding agent dissolved soluble material the absorption of charcoal.Simultaneously, this method estimates to provide the most effective utilization of Wetting Solution.

In case after this Wetting Solution-granular activated charcoal-binder mixtures preparation, it forms by being compacted to desired shape.Compacting and formation can be undertaken by using technology and the industrial technology be familiar with as those technician in the association area.These technology can comprise that the mixture compression enters in the cavity of matrix die head or mould.Additionally, mixture can be extruded by using various known technology.In forming process, enough pressure should put in the semi-plastic mixture to remove any air pocket that is embedded or big void space, makes SSACS have the structure than uniform density.Best, think in forming process, should apply enough pressure, so that semi-plastic wet binding element forces the cross connection of this carbon granules and these particulates to touch basically.The excessive binding agent or the use of wetting liquid can prevent that this type of carbon from contacting with carbon granule.The result of the binding agent that this is excessive or the use of wetting liquid is the SSACS intensity that reduces, density, or electroconductibility.

More highdensity if desired SSACS then applies higher compaction pressure, but the fragmentation of each carbon granules can take place.Wish that generally it is the needed pressure of each carbon granules of fragmentation that institute's applied pressure is no more than.This fragmentation can cause forming the SSACS with reduction in-plant transportation characteristic.Typically, to be found for pitch coal basal granule shape activation charcoal be gratifying to the pressure of 200-600 pound/square inch (psi).The granular activated charcoal of other type can be broken under different pressure.The pressure that is lower than about 200psi can cause forming the SSACS with limited physical strength.The compaction pressure that is higher than 600psi can use, but the fragmentation of each carbon granules can take place.Although in forming process mixture is exerted pressure, especially when use forming die head, the observations of unconjugated Wetting Solution can be used as a kind of indication, in mixture the amount of this solution too high with should reduce.Similarly, show that for the observations of bonded wet binding element the binder amount of initial mixture is too high and should reduce.

In case mixture has suitably formed required structure, this SSACS is randomly dry.This drying can be removed wetting liquid (typically being water) and be eliminated the semi-plastic character of SSACS, and its is understood hardening and typically demonstrates higher physical strength.The drying of SSACS can be undertaken by any known method, as long as the mechanical system degraded does not take place in drying process SSACS.Suitable method can include, but not limited to dry air, oven drying at high temperature, vacuum-drying, or lyophilize.Preferred drying temperature is about 100 ℃, when water is used as wetting liquid.Higher or lower temperature can both be used.Under about 100 ℃, some binding substancess of carbonization reagent and binding agent can cause the partial carbonization of binding agent.Under higher drying temperature, it is more serious that this carbonization can become.But even part or carbonization completely take place, this carbonization estimates can not influence the final performance of SSACS.After drying, SSACS is heating under inert or the other non-oxidizing condition under more than or equal to about 300 ℃ temperature basically.Wish that this heating can carry out under inertia or other non-oxidizable condition basically (comprising contact atmosphere), with oxidation and the relevant gasification that prevents SSACS.This type of oxidation and gasification can cause the outward appearance of difference of the SSACS that forms and the decline of mechanical integrity.

Additionally, this drying step can be removed with wetting SSACS by direct heating to greater than about 300 ℃ temperature.Yet, if drying step is removed, must careful operation.Wet SSACS contains relatively large volatility wetting liquid.Simultaneously, SSACS will distribute other material of significant quantity, when being heated to high temperature.This gaseous substance can comprise from byproduct in the calcining of carbonization reagent and the volatile matter that discharges from binding agent in carbonization/calcination process.If preparation SSACS is so that it has very fine and close structure and the raising of carbonization/calcining temperature is fast, then the inside of SSACS can experience the bigger raising on pressure, owing to emitting fast of gaseous substance.This pressure improves can cause almost that SSACS explodes fiercely.

SSACS to be heated to or be higher than about 300 ℃ top temperature and select for the desired properties of the finished product SSACS.It is generally acknowledged that the remarkable carbonization of binding agent mainly takes place under up to about 500-600 ℃ temperature.Therefore must suppose that the SSACS that is exposed to the top temperature that is lower than 500 ℃ can contain partially carbonized binding agent.Estimate that also transport property in the SSACS of the SSACS for preparing is because this partially carbonized binding agent and variation in these temperature ranges.After this manner, even this SSACS can show high mechanical strength, these SSACS use in some applications is limited.SSACS be heated to about 500 ℃ and be lower than top temperature between about 900 ℃ can eliminate the problem relevant with the partial carbonization of binding agent and be heated to higher temperature and compare and have some economic advantages.The SSACS for preparing in this temperature range typically shows the physical strength of reduction, but improved electroconductibility is arranged, and compares with those SSACS of preparation at a lower temperature.SSACS is heated to about 900 ℃-Yue 1000 ℃ temperature can cause forming a kind of SSACS, and it has unusual good mechanical strength and its electroconductibility is significantly higher than the electroconductibility of using those prepared products of lesser temps.In addition, the binding agent that contained in being heated to the SSACS of these comparatively high tempss derives from coke unusual porous seemingly.Therefore use the prepared SSACS of these higher Heating temperatures should have transport property in the very good particle.Based on these trend, can expect that the use of 1000 ℃ or higher carbonization/calcining temperature only further improves intensity and the conductivity of the SSACS that forms.Therefore, the preferred top temperature that SSACS was heated to is equal to or greater than about 900 ℃.No matter selected top temperature, the process of recommending SSACS to be heated to greater than about 300 ℃ any temperature under the top and bottom is to carry out in the inert atmosphere basically with regard to the oxidation of carbon.

SSACS is heated to more than or equal to the process of about 300 ℃ temperature and can finishes by using the Equipment for Heating Processing (stove) of operating in the isothermal mode.Additionally, this SSACS can be exposed to the temperature range that improves gradually by using this equipment.This temperature range can raise gradually for time or distance/space (being the gentle slope).Under the top and bottom, this kind equipment should be equipped with heating chamber the inert equipment and the oxidation that therefore prevents SSACS basically of making.

The residence time of SSACS needs not to be over-drastic under top temperature.Though right and wrong are obsessive, usually preferably, the inside and outside volume of SSACS has even performance.This homogeneity is by having enough residence time under top temperature, realizing so that the SSACS of whole parts reaches this temperature.Therefore the minimum residence time is typically depended on SSACS granularity and configuration.Because heat mainly is transferred by SSACS by conduction, enough residence time that must be provided under the highest elevated temperature are under the identical temperature with the inside and outside volume of guaranteeing SSACS.

The granularity that has been found that SSACS after being exposed to required top temperature can be lower than the shown granularity that goes out before this exposure.Typically, this " shrinking percentage " is several at the most percentage ratios.This contraction can be eliminated potentially by reduce the binding agent and/or the Wetting Solution volume that use in the preparation of SSACS.Additionally, the granularity of moistening compacting SSACS can be regulated for this shrinking percentage, if having the height accurate dimensions SSACS be desire.This adjusting can be passed through die head, mould, and forcing machine, or the miscellaneous equipment that is used for compacting and forms this SSACS carries out.

After SSACS was heated to required top temperature, SSACS should be from high temperature cooling to about envrionment temperature under inert condition basically.If this cooling is not to carry out in this heating unit, then precondition be in any transfer process between two equipment and/or whenever the temperature of SSACS greater than about 300 ℃ and more preferably prevent that this SSACS is exposed to air (oxygen) during envrionment temperature.In case cooling, this SSACS can choose wantonly and be washed to remove any carbonization agent residues, if desire.

The granular activated charcoal of 10 (weight) part is wetting with 10% aqueous solution of ammonium chloride in a preferred embodiment of the invention.The amount of ammonium chloride solution should make this carbon be moistening visibly and a spot of solution by visible outside this carbon granules.Then, six parts wheat-flour is joined in this moistening carbon.This binding substances is mixed, visually is transparent so that this carbon granules scribbles wet wheat-flour equably and do not have unconjugated solution.This mixture is added in the shaping die and compacting under the pressure of 300psi then.The SSACS of formed thereby takes out from die head, is positioned in the baking oven and down dry at 100 ℃ subsequently.After drying, this SSACS is added in the stove of (anaerobic basically) atmosphere that has inertia and 1000 ℃ of heating 20 minutes down.When 20 minutes times finished, SSACS was transferring to cooling room in the inert atmosphere basically from stove.Be cooled in the atmosphere of inertia (anaerobic basically) and be lower than after about 300 ℃, this SSACS takes out from cooling room.

The narration of embodiment

Embodiment 1 has illustrated that this starch adesive is not suitable among the present invention.Embodiment 2 has illustrated that binder material of the present invention is used for the purposes of the production of self-supporting activation carbon structure body.Embodiment 3 has illustrated that the granularity that has between 4 and 325 orders and the granular activated charcoal of the various distributions of granularity in this scope can be used among the present invention.Embodiment 4 has illustrated that various carbonization reagent can be used among the present invention.Embodiment 5 has illustrated the effect of using the carbonization reagent of selected amount in enforcement of the present invention.Embodiment 6 has illustrated the effect of using the binding agent of selected amount in enforcement of the present invention.Embodiment 7 has illustrated the typical result of force of compression (being pressure) to acquisition SSACS performance.Embodiment 8 illustrated the top temperature that will be heated at SSACS and obtain typical relation between the SSACS performance.Embodiment 9 has illustrated that the activity of granular activated charcoal is not seriously influenced by method of the present invention.Embodiment 10 has illustrated that big SSACS can be used for preparing by of the present invention making.Embodiment 11 has illustrated that cellular SSACS can be used for preparing by of the present invention making.For whole embodiment, unless otherwise mentioned, complete soln is that the aqueous solution and whole percentage compositions are by weight.

Embodiment

Embodiment 1: unless otherwise mentioned, otherwise follow procedure is used for producing activation charcoal SSACS.

Program: six parts granular activated charcoal respectively is about 5.00 grams, mixes with wetting liquid or the Wetting Solution of about 6.1ml separately.In these activation charcoal-wetting liquid/solution mixtures each is added the binding agent of about 4.00 grams.The mixture that is obtained mixes independently, till showing uniform the composition separately.That this activation charcoal-binding agent-Wetting Solution mixture is clamminess typically a little and demonstrate semi plastic matter at this moment.After this mixing, each several part is placed in the columniform shaping die by oneself and came compacting 3 minutes by the use hydropress under 500 pounds power.Cylindrical die by three parts be the die head body and up and down the punching press piston form.The hollow cylinder that the die head body is made up of ultrahigh molecular weight polyethylene(UHMWPE).The die head body has about 1 and 1/8 inch internal diameter, about 3 and 1/8 inches external diameter and about 2 and 3/4 inches height.The punching press piston is to be constituted and had about 1 and 1/8 inch external diameter by steel up and down.The external diameter of these punching press pistons (ram) is by applying glue, so that they provide the sucking fit to die head body inwall, in the time of in inserting the die head body.The height of following punching press piston is that about 3/4 inch height with last punching press piston is about 3 and 1/4 inches.After taking out in compacting with from die head, formed wetting SSACS be positioned over then in the baking oven that is under about 100 ℃ in case carry out one night drying.After drying, dry SSACS be placed in the crucible of cover lid and in retort furnace in inert atmosphere basically in about 950 ℃ of about 20 minutes stove residence time of calcining down.After calcining, SSACS is transferred in the cooling room and is being cooled to about envrionment temperature in the inert atmosphere basically in cooling room.For calcining and cooling, inert atmosphere is by allowing nitrogen gas stream flow through retort furnace or cooling room provides basically.The use of the crucible of cover lid further is suppressed at any air (oxygen) exposure in the heat-processed, the transfer of SSACS or cooling.Typically, formed SSACS is about 1 and 1/8 inch diameter and about 0.7 inch height.

Usually, after calcining and cooling, for having quality, diameter and the height of measuring each SSACS for those SSACS of relevant inferior limit disposal (handling) needed sufficient intensity (being mechanical integrity).SSACS density is calculated by using these data.Usually do not collect height and diameter data for the SSACS that does not demonstrate the cylindrical shape of good shaping because of cracking, foaming or swelling.Crushing strength is also measured for those SSACS with the clearly demarcated shape of outline usually.By at Spring Dial CompressionGauge (RIMAC Spring Tester, Model T4-0070, the 0-1000lbs scope, Rinck-McIlwaine, Inc., 69Armour Place, P.O.98, Dumont, NewJersey 07628) go up and place each SSACS between two parties, so that the main shaft of cylindrical SSACS is coaxial with the compelling force vector, measure crushing strength.The handle (handle) of Spring Dial Compression Gauge stably forces down then, till SSACS breaks.Exert pressure for the SSACS that breaks is needed and to read from tensimeter " maximum value-reading pointer " then.For the given sample sets (i.e. those that make in the same manner) of six kinds of SSACS, collected data average out and measure relevant standard deviation.

By using aforesaid program, by using Zulkovsky starch, tapioca (flour) or maltose-dextrin starch prepares activation charcoal SSACS as binding agent.This wetting liquid or Wetting Solution are water, 10.0%NH ₄Cl, 5.00% (NH ₄) ₂HPO ₄, 10.0% (NH ₄) ₂HPO ₄Or 15.0% (NH ₄) ₂HPO ₄This activation charcoal is a granulated material.This granular activated charcoal has been characterized by and has had 12 * 20 purpose nominal mesh sizes that (granularity that refers to this carbon is lower than 12 orders and greater than 20 orders, two mesh sizes are all according to the U.S.Sieve Series), 0.507g/cc apparent density (Calgon Carbon Test Number 7, Calgon Carbon Corp., Pittsburgh, PA), 1.29mm median size (Calgon Carbon Test Number 9, CalgonCarbon Corp., Pittsburgh, PA), iodine number (Calgon CarbonTest Number 4 with 1196mg/g, Calgon Carbon Corp., Pittsburgh, PA).The performance of the SSACS that is obtained is shown in Table 1.

As shown in table 1, the binding substances of listed binding agent and wetting liquid or Wetting Solution all obtains to have kept the SSACS of the clearly demarcated cylindrical exterior of their outline predetermined and that just formed.For whole three kinds of binding agents, make water can form so weak (shortage mechanical integrity) so that the SSACS that also disintegrates basically with minimal disposal (handling) as the preparation method of wetting liquid.Use three kinds of different binding agents and 10.0%NH ₄How many better mechanical strength prepared those of Cl have shown and can collect mass data for some binding substancess of binding agent and wetting liquid.For these SSACS, the average quality value is shown in Table 1 with relevant standard deviation.But, be noted that whole these SSACS demonstrate the physical form of distortion.Swelling takes place in some in drying and/or calcination process, make the initial cylindrical shape of SSACS be distorted.Similarly, other then bubbles to such degree, promptly cylindrical shape fully twist and the aggregate material that obtained seemingly more or less spherical in shape.Several in these preparations, some of them are to make as the replica of other sample sets, it is so weak so that stop follow-up calcining being judged after oven drying.Therefore,,, even combine, bond after acceptable or enough calcinings of granular activated charcoal are not provided with selected carbonization reagent by the starch of prior art instruction by the data acknowledgement that provides in the table 1.

Table 1

Use the performance of selected starch as the SSACS of adhesive preparation

Sample group Ref. No.	Binding agent	Wetting liquid or solution	Calcination SSACS outward appearance	Average calcination SSACS quality (g)	Average calcination SSACS density (g/cc)	Average calcination crushing strength (lbs)
							3285-23	Zulkovsky starch	H 2O	Disintegration	-	-	-
3285-23	″	10.0％NH 4Cl	Bubble	5.94+/-0.03	-	-
							3285-22	″	10.0％NH 4Cl	Too weak can't the calcining	-	-	-
3285-34	″	5.00％(NH 4) 2HPO 4	Swelling	5.82+/-0.02	-	-
							3285-66	″	10.0％(NH 4) 2HPO 4	Serious swelling	5.95+/-0.02	-	-
3285-44	″	10.0％(NH 4) 2HPO 4	Too soft can't the calcining	-	-	-
							3285-56	″	15.0％(NH 4) 2HPO 4	Too soft can't the calcining	-	-	-
3285-62	Tapioca (flour)	H 2O	Disintegration	-	-	-
							3285-29	″	10.0％NH 4Cl	Swelling	5.34+/-0.32	-	-
3285-28	″	10.0％NH 4Cl	Too weak can't the calcining	-	-	-
							3285-52	″	10.0％NH 4Cl	Too weak can't the calcining	-	-	-
3285-53	″	5.00％(NH 4) 2HPO 4	Slight swelling	5.69+/-0.04	-	-
							3285-89	″	10.0％(NH 4) 2HPO 4	Swelling	5.86+/-0.02	-	-
3285-45	″	15.0％(NH 4) 2HPO 4	Swelling	6.03+/-0.02	-	-
							3287-10	Maltose-dextrin starch	H 2O	Disintegration	-	-	-
3285-13	″	10.0％NH 4Cl	The serious foaming	5.95+/-0.12	-	-
							3285-12	″	5.00％(NH 4) 2HPO 4	Swelling	5.77+/-0.02	-	-
3287-8	″	10.0％(NH 4) 2HPO 4	Serious swelling	5.90+/-0.03	-	-
							3285-43	″	15.0％(NH 4) 2HPO 4	Swelling, cracking	6.05+/0.05	-	-

Embodiment 2: use the granular activated charcoal that provides among the embodiment 1, wetting liquid or solution and program prepare SSACS and characterize.The preparation of these SSACS is different from those of embodiment 1 on selection of binder.The binding agent that is used to prepare the SSACS of this embodiment is the various examples of these materials.Selected these examples of material as binding agent are wheat-flours, oatmeal, Spelt powder, Semen Maydis powder (the slight stir-fry bakes), ground rice, barley meal, buckwheat flour, rye meal, and potato powder.With the respectively performance of the SSACS of group of these adhesive preparation, the standard deviation with relevant is shown in Table 2.

As shown in table 2, wheat-flour (belonging to the type that is generally used for toasting purpose) is produced (edge that outline is clearly demarcated that has good appearance, surperficial uniformly, there is not the remarkable cracking of visible, almost not activating carbon particle peels off from SSACS is lip-deep) and the SSACS of 40lbs crushing strength, when water during as wetting liquid.When 10.0% ammonium chloride replaced water in this prescription, SSACS quality, density and crushing strength all improved significantly, compared with those SSACS that make the water preparation.When being used as Wetting Solution, ammonium dibasic phosphate solution observes similar raising.Can point out that also SSACS quality, density and crushing strength are all along with improving as the raising of the concentration of the Secondary ammonium phosphate of Wetting Solution.Spelt powder (Spelt is the durum wheat of particular type) as desired, is produced the SSACS that has with those performance similar performance of using the common wheat powder to be produced.

Table 2 also shows, use oatmeal and rye meal as the listed performance of the prepared SSACS of binding agent generally shown form speech with regard to wetting liquid with those identical trend that prepare from wheat-flour.Specifically, these trend are different from uses observed those of wheat-flour, with regard to higher SSACS quality and lower SSACS density and crushing strength.

Whole other binding agents (Semen Maydis powder, ground rice, barley meal, buckwheat flour, and potato powder) that are used for this embodiment have shown by at least some swellings of at least a generation in selected wetting liquid or the Wetting Solution.Yet these results show that the wisdom that wetting liquid or Wetting Solution are formed is selected and can be stoped, and for these binding agents, SSACS is swelling by calcining.The investigation of table 2 shows that also in general, it is more effective than ammonium chloride aspect minimizing SSACS swelling that Secondary ammonium phosphate is proved to be.Be apparent that also the SSACS crushing strength is along with the concentration of carbonization reagent in wetting liquid improves and improves.In addition, obviously be that the use that contains the carbonization reagent of wetting liquid can significantly improve the SSACS quality, density, and crushing strength.This raising has illustrated that the use of carbonization reagent in wetting liquid can cause higher coke yield after calcining.Also should be noted that, use those the prepared SSACS of 10% Secondary ammonium phosphate that contain Wetting Solution to show those the prepared higher average calcination SSACS crushing strengths of 10% ammonium chloride that contain Wetting Solution than using.This in addition more outstanding behaviours do not have too many difference for " the on average calcination SSACS quality " of the sample sets by using the preparation of these two kinds different carbonization reagent place.These results have indicated that the use of Secondary ammonium phosphate carbonization reagent in wetting liquid can cause forming stronger amylaceous material (starchy-material) coke of deriving, or this coke is compared as the result that carbonization reagent place obtains with use ammonium chloride in Wetting Solution the stronger bonding of granular activated charcoal.

Therefore, the data declaration that provides in table 2, binder material of the present invention can be used in produces SSACS, different with the starch of being instructed by prior art.

Table 2

Use cereal and stem tuber powder performance as the prepared SSACS of binding agent

Sample group Ref. No.	Binding agent	Wetting liquid or solution	Calcination SSACS outward appearance	Average calcination SSACS quality (g)	Average calcination SSACS density (g/cc)	Average calcination SSACS crushing strength (lbs)
							3285-3	Wheat-flour	H 2O	Well	5.53+/-0.02	0.526+/-0.003	40+/-2
3285-2	Wheat-flour	10.0％NH 4Cl	Very good	5.97+/-0.03	0.556+/-0.005	178+/-3
							3285-85	Wheat-flour	5.00％(NH 4) 2HPO 4	Very good	5.86+/-0.02	0.574+/-0.004	206+/-9
3285-90	Wheat-flour	10.0％(NH 4) 2HPO 4	Very good	5.94+/-0.03	0.580+/-0.006	263+/-12
							3285-94	Wheat-flour	15.0％(NH 4) 2HPO 4	Very good	6.05+/-0.04	0.594+/-0.006	355+/-9
3285-5	Oatmeal	H 2O	Well	5.59+/-0.02	0.508+/-0.007	26+/-3
							3285-4	Oatmeal	10.0％NH 4Cl	Well	6.14+/-0.02	0.532+/-0.003	80+/-6
3285-84	Oatmeal	5.00％(NH 4) 2HPO 4	Well	6.17+/-0.01	0.552+/-0.004	102+/-4
							3285-91	Oatmeal	10.0％(NH 4) 2HPO 4	Very good	6.29+/-0.04	0.552+/-0.004	137+/-3
3285-95	Oatmeal	15.0％(NH 4) 2HPO 4	Well	6.39+/-0.04	0.556+/-0.005	157+/-9
							3285-7	Semen Maydis powder	H 2O	Swelling, cracking	-	-	-

3285-6	Semen Maydis powder		10.0％NH 4Cl	Swelling	6.10+/-0.02	-	-
									Semen Maydis powder		5.00％(NH 4) 2HPO 4	Very good	6.10+/-0.01	0.500+/-0.005	87+/-5
3285-39	Semen Maydis powder		10.0％(NH 4) 2HPO 4	Well	6.16+/-0.01	0.511+/-0.008	97+/-7
								3287-2	Semen Maydis powder		15.0％(NH 4) 2HPO 4	Very slight swelling	6.37+/-0.03	0.514+/-0.010	93+/-14
3285-9	Rice meal		H 2O	Very slight swelling	5.58+/-0.03	-	-
								3285-8	Rice meal		10.0％NH 4Cl	Swelling	6.15+/-0.00	-	-
3285-63	Rice meal		5.00％(NH 4) 2HPO 4	Very good	6.08+/-0.01	0.532+/-0.006	181+/-10
								3285-40	Rice meal		10.0％(NH 4) 2HPO 4	Well	6.23+/-0.02	0.540+/-0.004	169+/-3
3285-59	Rice meal		15.0％(NH 4) 2HPO 4	Very good	6.40+/-0.02	0.554+/-0.007	185+/-9
								3285-25	Barley meal		H 2O	Well	5.64+/-0.01	0.502+/-0.001	23+/-1
3285-24	Barley meal		10.0％NH 4Cl	Very slight swelling	6.01+/-0.03	-	-
								3285-65	Barley meal		5.00％(NH 4) 2HPO 4	Very good	6.05+/-0.03	0.535+/-0.006	111+/-6
3285-42	Barley meal		10.0％(NH 4) 2HPO 4	Very good	6.18+/-0.03	0.540+/-0.007	145+/-6
								3285-61	Barley meal		15.0％(NH 4) 2HPO 4	Very slight swelling	6.32+/-0.04	0.530+/-0.007	155+/-14
3285-15	Buckwheat flour		H 2O	Swelling, soft	5.49+/-0.02	-	-
								3285-14	Buckwheat flour		10.0％NH 4Cl	Swelling	6.11+/-0.02	-	-
3285-64	Buckwheat flour		5.00％(NH 4) 2HPO 4	Very good	5.98+/-0.03	0.517+/-0.009	174+/-25
								3285-41	Buckwheat flour		10.0％(NH 4) 2HPO 4	Well	6.09+/-0.03	0.516+/-0.007	195+/-9
3285-60	Buckwheat flour		15.0％(NH 4) 2HPO 4	Slight swelling	6.24+/-0.02	-	-
								3285-21	Rye meal		H 2O	Well	5.58+/-0.02	0.489+/-0.003	14+/-2
3285-20	Rye meal		10.0％NH 4Cl	Well	6.24+/-0.01	0.522+/-0.005	49+/-5
								3285-87	Rye meal		5.00％(NH 4) 2HPO 4	Very good	6.18+/-0.01	0.520+/-0.005	48+/-1
3285-92	Rye meal		10.0％(NH 4) 2HPO 4	Well	6.38+/-0.03	0.542+/-0.004	87+/-5
								3287-3	Rye meal		15.0％(NH 4) 2HPO 4	Very good	6.51+/-0.03	0.550+/-0.003	115+/-3

3285-27	The Spelt powder	H 2O	Well	5.76+/-0.03	0.532+/-0.006	74+/-6
							3285-26	The Spelt powder	10.0％NH 4Cl	Well	6.05+/-0.01	0.548+/-0.007	94+/-4
3285-88	The Spelt powder	5.00％(NH 4) 2HPO 4	Very good	6.00+/-0.03	0.561+/-0.008	160+/-4
							3285-93	The Spelt powder	10.0％(NH 4) 2HPO 4	Very good	6.13+/-0.03	0.586+/-0.007	267+/-11
3287-4	The Spelt powder	15.0％(NH 4) 2HPO 4	Very good	6.32+/-0.02	0.591+/-0.004	334+/-7
							3285-11	Potato powder	H 2O	Swelling, cracking	5.74+/-0.02	-	-
3285-10	The Ma Lingzhu powder	10.0％NH 4Cl	Very good	6.22+/-0.02	0.542+/-0.005	173+/-10
							3287-7	Potato powder	5.00％(NH 4) 2HPO 4	Very good	6.07+/-0.02	0.527+/-0.010	140+/-10
3287-9	Potato powder	10.0％(NH 4) 2HPO 4	Very good	6.32+/-0.03	0.545+/-0.004	204+/-5
							3287-5	Potato powder	15.0％(NH 4) 2HPO 4	Very good	6.42+/-0.03	0.549+/-0.003	239+/-11

Embodiment 3: have the median size of 3.18mm, nominal 4 * 6 order granular activated charcoals of the iodine number of 958mg/g and the apparent density of 0.518g/cc are broken and/or screen with production and have 4 * 6,6 * 10, the granular activated charcoal of 10 * 20,20 * 80 and 80 * 325 mesh sizes.Simultaneously, each in these size of mesh fractions of equal in quality part is had 4 * 325 mesh sizes activation charcoal of known median size with production by blending.Have each six parts granular activated charcoal in these size of mesh fractions by adopting the program in embodiment 1, provide, but three exceptions are arranged, be used to produce SSACS.First exception is that this compaction pressure is 300lbs.Second exception is that the volume that is used to form the Wetting Solution of SSACS is: about 4.5ml for 4 * 6 mesh size carbon fractions, 4.7ml for 6 * 10 mesh size carbon fractions, 4.9ml for 10 * 20 mesh size fractions, 5.1ml for 20 * 80 mesh size fractions, for 5.5ml for 80 * 325 mesh size fractions and for 4 * 325 mesh size fractions 5.1ml.With the 3rd exception be about 3.00 the gram binding agents be used to prepare each SSACS.The SSACS that is obtained is also by using the method for describing in embodiment 1 to characterize.

Specifically, water or 10.0% ammonium chloride solution are as the wetting liquid or the solution of each mesh size fraction of granular activated charcoal.This binding agent is a wheat-flour.

Table 3 has shown the average properties and relevant standard deviation of the sample sets of the SSACS of preparation by this way.As shown in Table, to be judged be medium to the outward appearance of the SSACS by using 4 * 6 and 6 * 10 mesh size carbon preparations.As if these SSACS show very uneven surface texture and do not have too big mechanical integrity.Because the big relatively median size of big sieve mesh carbon, how much uneven surface texture of these SSACS can expect.Can't measure reliably from the crushing strength of the SSACS of 4 * 6 and 6 * 10 mesh size carbon preparations, because it can not clearly be measured to when along with improving compelling force during recurring structure destruction.But, as shown in this embodiment, might use these big mesh sizes/median size activation charcoal to make activation charcoal SSACS.On the other hand, less activation charcoal mesh size/median size can be produced and have good SSACS to excellent appearance.It is pointed out that also the crushing strength of relevant SSACS improves significantly along with median size descends.

As the previous embodiment, the use of carbonization reagent (being ammonium chloride in this case) can cause forming higher binding agent coke productive rate and may be stronger coke.Higher binding agent coke productive rate is by proving in the qualitative difference of SSACS between those sample sets of the preparation of water only and those sample sets of using aqueous ammonium chloride solution to prepare as Wetting Solution.Binding agent coke intensity that may be higher is by making water as the shown constant relatively crushing strength of the sample sets of wetting liquid preparation-to (versus)-indicated by the shown carbon mesh size/median size dependency crushing strength of those SSACS of using carbonization reagent (ammonium chloride) preparation in Wetting Solution.The crushing strength that also is noted that the SSACS that uses the preparation of 4 * 325 mesh sizes activation charcoal is higher than median size and those median sizes of narrow mesh size activation charcoal and the result that the crushing strength contrast is estimated who activates charcoal from theme.This result is considered to and activates charcoal filling effect (shown by the remarkable apparent density difference between 4 * 325 sieve mesh materials and other size fraction) and relevant with the size of accumulation outer surface area of each activation carbon particle.

Table 3

The performance of the SSACS that the selected mesh size of use granular activated charcoal is prepared

Sample group Ref. No.	The kryptol mesh size	The apparent close change of kryptol (g/cc)	Kryptol median size (mm)	Wetting liquid or solution	Calcination SSACS outward appearance	Average calcination SSACS quality (g)	Average calcination SSACS density (g/cc)	Average calcining SSACS crushing strength (lbs)
									3285-74	4×6	0.51	3.71	H 2O	Medium	5.67+/-0.00	0.535+/-0.005	-
3285-67	″	″	″	10％NH 4Cl	Medium	6.16+/-0.03	0.547+/-0.010	-
									3285-75	6×10	0.505	2.88	H 2O	Medium	5.60+/-0.02	0.510+/-0.008	-
3285-68	″	″	″	10％NH 4Cl	Medium	6.17+/-0.01	0.538+/-0.009	-
									3285-76	10×20	0.509	1.22	H 2O	Well	5.67+/-0.01	0.522+/-0.003	50+/-3
3285-69	″	″	″	10％NH 4Cl	Well	6.21+/-0.02	0.569+/-0.007	140+/-2
									3285-77	20×80	0.519	0.56	H 2O	Excellent	5.67+/-0.00	0.514+//-0.008	103+/-8
3285-72	″	″	″	10％NH 4Cl	Excellent	6.20+/-0.01	0.593+/-0.005	293+/-13
									3285-78	80×325	0.474	0.22	H 2O	Excellent	5.68+/-0.02	0.500+/-0.003	63+/-4
3285-73	″	″	″	10％NH 4Cl	Excellent	6.19+/-0.01	0.580+/-0.004	442+/-37
									3287-16	4×325	0.616	1.72	H 2O	Well	5.54+/-0.01	0.535+/-0.011	73+/-9
3287-11	4×325	″	″	10％NH 4Cl	Well	6.10+/-0.03	0.604+/-0.008	281+/-45

Embodiment 4: have the apparent density of 0.394g/cc by use, 12 * 40 sieve mesh granular activated charcoals of the median size of 1.11mm and the iodine number of 1312mg/g prepare SSACS.The wetting liquid or the solution that are used for the preparation of these SSACS are H ₂10.0% solution of O and selected carbonization reagent.Selecting the carbonization reagent of usefulness is ammonium chloride, ammonium iodide, brometo de amonio, ammonium sulfate, phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate and zinc chloride.The program that is used for preparing these SSACS provides at embodiment 1, just except the improvement below.The first, being used to prepare the wetting liquid of each SSACS or the amount of solution is about 6.7 grams.Secondly, this carbon-binding agent-wetting liquid/solution mixture is by the power of use 300lbs, rather than the power of 500lbs, comes compacting.The 3rd, the binding agent quality of each SSACS is about 3.00 grams.With the 4th, Carver Model " C " lab press (the Fred S.Carver Inc. of 0-500lbs load gauge is housed, P.O.Box 428, MenomoneeFalls, WI 53051-0428) replace being used for the Spring DialC0mpression Gauge of the mensuration of crushing strength.Wheat-flour is as this binding agent.

Zhi Bei the selected average behaviour of respectively organizing SSACS by this way, the standard deviation with relevant provides in table 4.The investigation of these data shows that 10% zinc chloride solution can cause forming SSACS as Wetting Solution, and the latter's density equals to use H ₂O is significantly less than as wetting liquid obtained those and crushing strength and uses H ₂O is as crushing strength that wetting liquid obtained.Therefore obviously be that zinc chloride is not suitable for use in the carbonization reagent among the present invention.Adopt the Wetting Solution of other selected carbonization reagent can obtain to activate charcoal SSACS, density that the latter had and crushing strength be better than by water only as wetting liquid obtained those.Therefore the additive of selected carbonization reagent as wetting liquid be described, formed the benefit of Wetting Solution.It is pointed out that also various phosphate base carbonization reagent can form the SSACS with broken intensity of observed maximal pressure in this embodiment as the use of the solute in the Wetting Solution.This result shows that " crosslinked " effect of this type of reagent can be responsible for for this observed further improvement in SSACS intensity.

Table 4

Use the performance of the SSACS of selected carbonization reagent preparation

The sample group #	Wetting liquid or solution	Average calcination SSACS quality (g)	Average calcination SSACS density (g/cc)	Average calcination SSACS crushing strength (lbs)
					3165-96	H 2O	5.60+/-0.01	0.441+/-0.004	62+/-5
3256-03	10.0％ZnCl 2	5.88+/-0.02	0.441+/-0.003	25 *
					3165-95	10.0％NH 4Cl	5.92+/-0.01	0.461+/-0.005	140+/-5
3256-05/6	10.0％NH 4Br	5.91+/-0.02	0.447+/-0.005	101+/-8
					3287-22	10.0％NH 4I	5.87+/-0.00	0.440+/-0.006	130+/-8
3287-17	10.0％(NH 4) 2SO 4	5.84+/-0.01	0.433+/-0.003	106+/-8
					3256-04/5	10.0％H 3PO 4	5.98+/-0.01	0.453+/-0.007	215+/-11
3256-03/4	10.0％NH 4H 2PO 4	6.06+/-0.02	0.459+/-0.005	213+/-14
					3256-02	10.0％(NH 4) 2HPO 4	6.04+/-0.01	0.467+/-0.006	275+/-14

^*A data point

Embodiment 5: use the program of describing in embodiment 1 to prepare each SSACS that organizes and characterize.For the SSACS of whole these groups, wheat-flour is as this binding agent.Prepare seven groups SSACS.The preparation of these groups is different for the type of employed wetting liquid/solution.Employed seven kinds of wetting liquid/solution are listed in the table 5.

Zhi Bei the average properties of respectively organizing SSACS also provides in table 5 by this way.As shown in this table, " average calcination SSACS quality " is along with the concentration of carbonization reagent (Secondary ammonium phosphate) in Wetting Solution improves and improves.Should " average calcination SSACS density " and crushing strength also along with Wetting Solution Secondary ammonium phosphate concentration improves up to 20.0% value.Under 25.0% Secondary ammonium phosphate Wetting Solution concentration, " average calcination SSACS density " has shown that very slight decline and " average calcination SSACS crushing strength " descend widely from using those observed values of 20.0% Secondary ammonium phosphate Wetting Solution concentration.These presentation of results can expect that the carbonization reagent of a tittle causes having obtained the maximum value with regard to the improvement of the listed performance of the SSACS that obtained.

Table 5

Use the performance of SSACS of the given carbonization reagent preparation of selected amount

Sample group Ref. No.	Wetting liquid or solution	Average calcination SSACS quality (g)	Average calcination SSACS density (g/cc)	Average calcination SSACS crushing strength (lbs)
					3285-03	H 2O	5.53+/-0.02	0.526+/-0.003	40+/-2
3287-19	2.50％(NH 4) 2HPO 4	5.76+/-0.02	0.566+/-0.006	141+/-4
					3285-85	5.00％(NH 4) 2HPO 4	5.86+/-0.02	0.574+/-0.004	206+/-9
3285-90	10.0％(NH 4) 2HPO 4	5.94+/-0.03	0.580+/-0.006	263+/-12
					3285-94	15.0％(NH 4) 2HPO 4	6.05+/-0.04	0.594+/-0.006	355+/-9
3287-18	20.0％(NH 4) 2HPO 4	6.33+/-0.03	0.589+/-0.005	368+/-15
					3287-20	25.0％(NH 4) 2HPO 4	6.43+/-0.03	0.582+/-0.005	303+/-13

Embodiment 6: have the apparent density of 0.411g/cc by use, 12 * 40 sieve mesh granular activated charcoals of the median size of 1.08mm and the iodine number of 1286mg/g prepare SSACS.The Wetting Solution that is used for the preparation of these SSACS is 10.0% solution of Secondary ammonium phosphate.This binding agent is a wheat-flour.The program that is used for preparing these SSACS provides at embodiment 1, just except the improvement below.The first, the amount that is used for preparing the Wetting Solution of each SSACS provides at table 6.As shown in this table, the average quality of Wetting Solution improves along with the raising of binding agent quality.This raising of Wetting Solution is to guarantee that binding agent when blending and mixing-carbon formation semi plastic material is needed.Secondly, this carbon-binding agent-Wetting Solution mixture is by the power of use 300lbs, rather than the power of 500lbs, comes compacting.The 3rd, the binding agent quality of each SSACS provides in table 6.With the 4th, Carver Model " C " lab press (the Fred S.Carver Inc. of 0-500lbs load gauge is housed, P.O.Box 428, Menomonee Falls, WI 53051-0428) replace being used for the Spring Dial Compression Gauge of the mensuration of crushing strength.

The resistivity of the cylindrical activation charcoal SSACS that is obtained is measured in following mode.Aluminium sheet is placed the one side and the opposite face of another aluminium sheet against it against cylindrical SSACS.This aluminium sheet measurement size is about 1 and 1/2 inch and multiply by 2 and 1/2 inches and be 1/8 inch thickness.The orientation of this layout should make the front of SSACS separately that the plane determined by aluminium sheet fully covers it perpendicular to main shaft and each aluminium sheet of cylindrical SSACS.The non-conductive plastic insulation in side with those relative aluminium sheets that contact this carbon SSACS.Precondition is the attaching that the edge of each aluminium sheet is used for electrical lead.These electrical leads are connected in Keithley Model 580Micro-ohmmeter (KeithleyInstruments in one way, Inc., Cleveland, Ohio), this mode makes can utilize " 4-wire method (Wire Method) " to carry out measurement of resistance.In case this activation charcoal SSACS and aluminium sheet are orientated like that according to described, 50 pounds power are put on the subassembly so that the direction of this power is coaxial with the main shaft maintenance of cylindrical SSACS.Applying in the process of this power, measure the resistance of this subassembly by using Keithley Model 580Micro-ohmmeter.Because aluminium sheet can be ignored owing to the use of " 4-wire method " with the resistance that relevant point goes between, so measured resistance is got the resistance value of making this activation charcoal SSACS.Because expect that this activation charcoal SSACS is that electrical property is isotropic, the resistivity of carbon SSACS will be that SSACS resistance multiply by the product of cylindrical SSACS cross-sectional area again divided by the SSACS height.By this relation and measured SSACS resistance, the use of diameter and height, mensuration comprises the resistivity of the matrix material of each SSACS.For those SSACS that prepare in equal mode, altogether six kinds in this case, each resistivity of being measured by this method is by calculating mean value and measure the relevant standard deviation of this mean value.

The resistivity of granular activated charcoal that is used for the preparation of these SSACS is to be positioned in the cylindrical cavity that forms the non-conductive plastics of a slice by the above-mentioned carbon with about 5.0g to measure.The solid aluminum cylinder is loaded in the bottom of this cylindrical cavity.After the carbon sample is inserted in the cylindrical cavity, another solid aluminum cylinder is inserted in the cylindrical cavity, make carbon potential between the inner face of two aluminium cylinders.The aluminium cylinder has 1.125 inches diameter, and the diameter of it and cylindrical cavity closely mates, and is vertical through the main shaft with each cylinder after the machining with level and smooth end face.Precondition is the outer end that the requirement electrical lead is connected in each aluminium cylinder.These electrical leads should cylindrically be connected in Keithley Model 580 Micro-ohmmeter (KeithleyInstruments in one way, Inc., Cleveland, Ohio), this mode makes can utilize " 4-wire method (Wire Method) " to carry out measurement of resistance.Then 50 pounds power is put on the outside of aluminium cylinder.The vector of this power is parallel to the vector of the main shaft of aluminium cylinder.This power apply the compacting that can cause carbon between the inner face of aluminium cylinder.Applying in the process of this power, measure the resistance that crosses this compacting carbon sample.The resistivity of compacting carbon sample passes through to use this resistance value, aluminium cylinder diameter, and the distance between the inner face of aluminium cylinder is calculated in this carbon sample of compacting.In compacting carbon sample, be as calculating in the difference of the distance between the outside of aluminium cylinder in the presence of the compacting carbon sample and not in the distance between the inner face of aluminium cylinder.After this manner, the resistivity of carbon sample is that the product of the measured resistance cross-sectional area that multiply by aluminium cylinder inner face is divided by the distance between the inner face of aluminium cylinder in compacting process.The resistivity of the granular activated charcoal of the preparation of the SSACS that is used in the present embodiment being considered is 1.70ohm-cm.

The selected average behaviour of Zhi Bei SSACS by this way, the standard deviation with relevant provides in table 6.As shown in this table, " average calcination SSACS quality ", density and crushing strength all improve along with the raising of binding agent quality, though not necessarily in proportion." average calcination SSACS resistivity " descends till reaching the 3.00g binding agent always and keeps relative constant (if considering the standard deviation of " average calcination SSACS resistivity " data) then.Therefore, obviously the use of the increasing amount of binding agent can cause the SSACS density and the crushing strength that improve.Be apparent that also the binding agent that needs minimum quantity is to obtain the lowest resistivity of SSACS material, when using given program to prepare.Can not cause the further reduction of resistivity greater than the use of the binder amount of this minimum quantity.Be apparent that also the resistivity of SSACS is lower than the not resistivity of agglutinating granular activated charcoal.Therefore, the electroconductibility of SSACS can be superior to the electroconductibility of the not agglutinating packed bed of granular activated charcoal.

Table 6

Use the performance of the wheat-flour of selected amount as the SSACS of adhesive preparation

Sample group Ref. No.	Average quality binding agent (g)	Average quality Wetting Solution (g)	Average calcination SSACS quality (g)	Average calcination SSACS density (g/cc)	Average calcination SSACS resistivity (mohm-cm)	Average calcination SSACS crushing strength (lbs)
							3256-62	1.00+/-0.01	6.37+/-0.01	5.27+/-0.03	0.405+/-0.003	-	31+/-3 *
3256-63	2.00+/-0.01	6.75+/-0.02	5.73+/-0.02	0.445+/-0.006	351+/-10	120+/-13 *
							3256-64	3.00+/-0.01	6.92+/-0.02	6.12+/-0.01	0.470+/-0.004	266+/-20	226+/-9
3256-65	4.01+/-0.00	7.46+/-0.03	6.50+/-0.01	0.491+/-0.007	284+/-14	235+/-13
							3256-66	5.01+/-0.00	8.01+/-0.01	6.83+/-0.02	0.502+/-0.005	288+/-2	313+/-15

^*The mean value of five samples

Embodiment 7: have the apparent density of 0.394g/cc by use, 12 * 40 sieve mesh granular activated charcoals of the median size of 1.11mm and the iodine number of 1312mg/g prepare SSACS.The Wetting Solution that is used for the preparation of these SSACS is 10.0% solution of Secondary ammonium phosphate.This binding agent is a wheat-flour.The program that is used for preparing these SSACS provides at embodiment 1, just except the improvement below.The first, the quality that is used to prepare the Wetting Solution of each SSACS is about 7.2g.Secondly, the power that this carbon-binding agent-Wetting Solution mixture is listed in table 7 by use, rather than the power of 500lbs are come compacting.The 3rd, the binding agent quality of each SSACS is about 3.00g.With the 4th, Carver Model " C " lab press (the Fred S.Carver Inc. of 0-500lbs load gauge is housed, P.O.Box 428, Menomonee Falls, WI 53051-0428) replace being used for the Spring Dial Compression Gauge of the mensuration of crushing strength.

The resistivity of aforesaid granular activated charcoal is 1.49ohm-cm, measures by use the method that provides in embodiment 6.Simultaneously, average calcination SSACS resistivity is measured by use the method that provides in embodiment 6.

The average properties of respectively organizing SSACS for preparing in the above described manner and characterize provides in table 7.As shown in this table, the size of compaction force is for " average calcination SSACS quality " almost not influence.Therefore show that compaction force does not influence in carbonization and/or calcination process the various variations/reaction by binding agent experienced significantly.Yet, observe compaction force for having some influences in other SSACS performance shown in this table.For example, can observe, " average calcination SSACS density " generally improves along with the raising of compaction pressure.This is indicating, the compaction force of increase can little by little force the semi plastic binding agent to enter among the granular activated charcoal and in the space on every side.Average calcination SSACS resistivity, in the scope of relevant standard deviation, having shown along with increasing compaction force has little variation, until these power reach till 800 and 1000 pounds.The fragmentation meeting of this results suggest granular activated charcoal takes place under these higher power.Also be noted that the resistivity that significantly is lower than granular activated charcoal (from its preparation SSACS) for the whole measured resistivity shown in these SSACS." average calcination SSACS crushing strength " also improves along with the raising of compaction pressure.This filling that has shown above-mentioned space once more can take place.Also possible is that this space is filled the degree that can improve binding agent-granular activated charcoal contact and therefore caused stronger bonding.At last, " the calcination SSACS activation charcoal density of calculating " is illustrated in the density (being the density of SSACS, if there is not the relevant coke of binding agent to exist) of granular activated charcoal among the SSACS.Should be noted that " the calcination SSACS activation charcoal density of calculating " is by the quality (5.00g) that average calcination SSACS density be multiply by existing activation charcoal and the result is being calculated divided by " average calcination SSACS quality ".Obviously, the exactness of this calculating is based on following hypothesis: the mechanical loss of granular activated charcoal is insignificant in the preparation process of SSACS.Suppose that also the activation charcoal does not cause significant quality to change for the exposure of calcining temperature.Observe in table 7, the calcination SSACS activation charcoal density of calculating improves significantly, reaches till about 400 pounds up to this compaction force, and the speed of density increase descends significantly after this.The apparent density that is used to prepare the carbon of these SSACS is 0.394g/cc.At about 400 pounds and be higher than under about 400 pounds compaction force, the granular activated charcoal density in SSACS is the apparent density of initial granular activated charcoal basically.Under 800 and 1000 pounds compaction force, the carbon density in SSACS can surpass the apparent density of initial granular activated charcoal.This result shows, is used for some broken can generations of the granular activated charcoal of SSACS.Even be noted that the fragmentation that the granular activated charcoal has taken place in the preparation process of SSACS, this fragmentation can be observed the increase of SSACS density and electroconductibility subsequently for not influence of loading capacity.Under any circumstance, show significantly, might make the carbon SSACS that has with the same high granular activated charcoal density of density initial, bonding, granulous activation charcoal by the use of this method by these results.

Table 7

Use the performance of the SSACS of selected compaction force preparation

Sample group Ref. No.	Compaction force (lbs)	Average calcination SSACS quality (g)	Average calcination SSACS density (g/cc)	Average calcination SSACS resistivity (mohm-cm)	Average calcination SSACS crushing strength (lbs)	The calcination SSACS activation charcoal density of calculating (g/cc)
							3256-47	50	6.03+/-0.03	0.402+/-0.006	301+/-16	68+/-10	0.333
3256-46	100	6.05+/-0.03	0.422+/-0.007	305+/-11	98+/-15	0.349
							325645	200	6.04+/-0.03	0.451+/-0.006	291+/-12	195+/-7	0.373
3256-44	300	6.03+/-0.00	0.462+/-0.006	296+/-11	235+/-13	0.385
							3256-48	400	6.10+/-0.01	0.480+/-0.006	309+/-23	280+/-23	0.403
3256-49	600	6.10+/-0.01	0.492+/-0.011	298+/-22	316+/-33	0.403
							3256-50	800	6.04+/-0.02	0.495+/-0.007	284+/-9	327+/-16	0.410
3256-51	1000	6.04+/-0.02	0.503+/-0.004	263+/-21	360+/-14	0.416

Embodiment 8: have the apparent density of 0.394g/cc by use, 12 * 40 sieve mesh granular activated charcoals of the median size of 1.11mm and the iodine number of 1312mg/g prepare SSACS.The Wetting Solution that is used for the preparation of these SSACS is 10.0% solution of Secondary ammonium phosphate.This binding agent is a wheat-flour.The program that is used for preparing these SSACS provides at embodiment 1, just except the improvement below.The first, the quality that is used to prepare the Wetting Solution of each SSACS is about 7.2g.Secondly, this carbon-binding agent-Wetting Solution mixture comes compacting by the power of using 300lbs.The 3rd, the binding agent quality of each SSACS is about 3.00g.With the 4th, Carver Model " C " lab press (the Fred S.Carver Inc. of 0-500lbs load gauge is housed, P.O.Box 428, MenomoneeFalls, WI 53051-0428) replace being used for the Spring DialCompression Gauge of the mensuration of crushing strength.With the 5th, the highest high temperature that each SSACS touched is called calcining temperature, is a kind of in the numerical value of listing in table 8.Similarly, the exposure duration under each top temperature, be called calcination time, in table 8, provide.Point out that also for simplicity, all SSACS after being exposed to selected high temperature (no matter height of this temperature), being considered to calcination and this exposure and being considered to calcining.

The resistivity of aforesaid granular activated charcoal is 1.49ohm-cm, measures by use the method that provides in embodiment 6.Simultaneously, average calcination SSACS resistivity is measured by use the method that provides in embodiment 6.

The average properties of respectively organizing SSACS for preparing in the above described manner and characterize provides in table 8.As shown in showing at this, " average calcination SSACS quality " and " average calcination SSACS density " descends along with improving " calcining temperature ".These as a result most probable distribute owing to the increase of the volatile matter that from the carbonization/calcining of binding agent under the temperature that raises gradually, is produced.As if also observe, " average calcination SSACS volume " experienced very slight decline along with improving calcining temperature.The overall decline that runs through employed whole calcination temperature range (800 ℃) is to be lower than 6%.This little decline shows, binding agent mainly is not between the point of contact of granular activated charcoal and does not therefore stop this point of contact to contact with each other.

Table 6 also shows " average calcination SSACS resistivity ", belongs to an exception, descends along with improving calcining temperature.Obviously, the SSACS that under the highest calcining temperature, prepares tool electroconductibility.Also point out, by using about 700 ℃ or be lower than the resistivity of the packed bed of the not agglutinating granular activated charcoal that in the preparation of these SSACS, uses greater than the resistivity of the prepared SSACS of about 700 ℃ calcining temperature.

At last, " average calcination SSACS crushing strength " just " calcining temperature " shown opposite complex relationship.This complex relationship might be the several effects of interacting that produced.This type of effect comprise following these.The raising that improves viewed crushing strength for 200 ℃-300 ℃ calcining temperatures may be that the result of binding agent with the fs of additional strength given in carbonization.When calcining temperature decline of viewed crushing strength when 300 ℃ are brought up to 600 ℃ may be because binding agent derives from the result of the loss of distributing caused binding agent quality of volatile matter.Observed consistent relatively crushing strength is then indicated the carbonization fully basically in this temperature range of this binding agent in 600 ℃-800 ℃ temperature range.At last, the observed crushing strength that has increased in 800 ℃-1000 ℃ the temperature range if truly and not be that random events takes place, shows that coke generation thermal induction that binding agent derives from resets and form stronger coke.

Table 8

The performance of the activation charcoal SSACS that under different calcining temperatures, prepares

The sample group #	Calcining temperature (℃)	Calcination time (min)	Average calcination SSACS quality (g)	Average calcination SSACS volume (cubic inch)	Average calcination SSACS density (g/cc)	Average calcination SSACS resistivity (ohm-cm)	Average calcination SSACS crushing strength (lbs)
								3256-07	200	40	8.08+/-0.03	0.837	0.589+/-0.009	12.8+/-0.8	141+/-27
3256-08	300	40	6.99+/-0.02	0.823	0.518+/-0.014	3.45+/-0.37	371+/-49
								3256-09	400	40	6.70+/-0.01	0.818	0.500+/-0.014	5.27+/-0.93	324+/-54
3256-10	500	40	6.51+/-0.02	0.822	0.484+/-0.005	4.56+/-0.29	229+/-21
								3256-11	600	40	6.41+/-0.01	0.811	0.482+/-0.006	2.38+/-0.12	211+/-21
256-12	700	40	6.32+/-0.02	0.807	0.478+/-0.007	1.12+/-0.05	216+/-9
								3256-13	800	40	6.22+/-0.02	0.800	0.474+/-0.002	0.568+/-0.018	216+/-7
3256-14	900	20	6.06+/-0.02	0.806	0.460+/-0.010	0.361+/-0.013	231+/-19
								3256-15	1000	20	6.01+/-0.02	0.790	0.464+/-0.004	0.253+/-0.010	241+/-13

Embodiment 9: have the apparent density of 0.394g/cc by use, 12 * 40 sieve mesh granular activated charcoals of the median size of 1.11mm and the iodine number of 1312mg/g prepare SSACS.The Wetting Solution that is used for the preparation of these SSACS is 10.0% solution of ammonium chloride.This binding agent is a wheat-flour.The program that is used for preparing these SSACS provides at embodiment 1, just except the improvement below.The first, the quality that is used to prepare the wetting liquid of each SSACS is about 6.7g.Secondly, this carbon-binding agent-Wetting Solution mixture comes compacting by the power of using 300lbs.With the 3rd, the binding agent quality of each SSACS is about 3.00g.

In this way the average calcination quality of Zhi Bei six SSACS be 5.87+/-0.01g.These calcination SSACS has also shown the average crushing strength of 93+/-9 pound, and 0.437+/-mean density of 0.004g/cc.The average iodine number of these six kinds of SSACS be 1086+/-3mg/g.

According to given program, each among these SSACS prepares by the granular activated charcoal that uses 5.00g.Suppose this granular activated charcoal in preparation without any loss, greater than the calcination SSACS quality of 5.00g owing to carbonization/calcination binding agent and some possible carbonization agent residues.Can suppose that this carbonization/calcination binding agent minimally if any, is made contributions to the gross activity of activation charcoal SSACS.So the average iodine number of granular activated charcoal is that average calcination SSACS iodine number multiply by the product of average calcination SSACS quality again divided by 5.00g in each SSACS.This value (1086mg/g*5.87g/5.00g) equal then 1275+/-6mg/g.When this value during with the contrast of the iodine number (1312mg/g) of granular activated charcoal, clearly the granular activated charcoal after forming SSACS, kept it initial activity about 97%.

Embodiment 10: prepare bigger SSACS by at first the granular activated charcoal of 118.10g being mixed with 10.0 solution of the Secondary ammonium phosphate of 153.55g.This granular activated charcoal is nominal 12 * 20 sieve mesh materials, and it has shown the apparent density of 0.507g/cc and the iodine number of 1196mg/g.After the aqueous solution was dispersed on the neutralization of activation charcoal well, the wheat-flour of 94.48g was added in this activation charcoal-aqueous mixture.This activation charcoal-Wetting Solution-wheat-flour mixture is further mixed, up to wheat-flour and Wetting Solution be evenly dispersed in the carbon and carbon on till.The semi-plastic material that is obtained is positioned in the rectangular enclosure of metal forming die head.The rectangular enclosure of this die head body is determined to be about 2.3 inches wide and about 5.3 inches long.By using this die head, semi-plastic material comes compacting by 3550 pounds the power that use has been applied in about three minutes time.The direction of this power is perpendicular to the plane of rectangle die head body.After the dismounting of compacting and die head, the SSACS that is obtained be placed on then about 100 ℃ down in the baking ovens of operation in case carry out one night drying.After drying, drying is not calcined SSACS and is placed on stainless steel hot processing bag (" Sen/pak ", The Sentry Company, Foxboro MA) in and in retort furnace, under about 950 ℃, calcining in the inert atmosphere basically, reaches about 1 hour retort furnace residence time.The purpose that it may be noted that the stainless steel bag is to reduce at high temperature SSACS to the possibility of the adventitious exposure of air (oxygen).After calcining, the SSACS of pack takes out and puts into cooling room from retort furnace.SSACS is being cooled to about envrionment temperature in the inert atmosphere then basically.For calcining and cooling, inert atmosphere is by allowing nitrogen gas stream flow through retort furnace or cooling room provides basically.The SSACS that is obtained has the quality of 144.10g.The size of this SSACS is 2.27 inches wide, 5.17 inches long and 1.36 inches high.Dry, the size of incinerating SSACS is not respectively 2.28,5.27 and 1.38.Therefore, some slight contractions (～2%) take place in rectangle activation charcoal SSACS in calcination process.This SSACS has extraordinary, uniform outward appearance and does not become bad significantly through repeatedly disposal (handling).The result shows that the instruction of the application of the invention might produce bigger SSACS.

Embodiment 11: by 80 * 325 sieve mesh granular activated charcoals of 15.00g, 10.0% ammonium dibasic phosphate solution of the wheat-flour of 12.00g and 21.15g prepares cellular SSACS.This mixture stirs, till obtaining uniform semi plastic mixture.This semi-plastic mixture is added in the cylindrical die with 21 1/4 inch rodss and about 2.05 inches internal diameter then, and these rodss keep spaced apart coaxially around the cylindrical die cavity and with its main shaft.These positions of these rodss fix by the suitable mach groove in die head punching press piston.After mixture being positioned in the die head body, mixture comes compacting by the power of using the 600-700 pound.This power is applied in and reaches about 3 minutes on the mixture.The structure of formed thereby took out from die head and at about 100 ℃ of one nights of following oven drying.The dry structure that is obtained is dropped in the crucible of cover lid then, with the adventitious exposure of inhibition for air, and is heating 30 minutes under the inert conditions basically under 950 ℃.After this heating, the crucible that contains SSACS is put in the cooling room and in basic inert atmosphere and is cooled near envrionment temperature.The SSACS that is obtained has columniform shape, the quality of 18.8g and have 1.9 inches external diameter and 1.13 inches height.21 1/4 inch diameter cylindrical holes are present among this SSACS.These holes are along cylindrical SSACS and spaced apart coaxially with the main shaft maintenance of cylindrical SSACS.The intensity of the SSACS that is obtained is enough to bear disposal (handling) repeatedly.It is very good that the outward appearance of SSACS is judged, and wherein SSACS has shown the even outside surface that does not have visible crack.The result shows that the instruction of the application of the invention might produce cellular SSACS.

Although the front at length is described, embodiment and method are to provide not limited significance for the purpose of illustrating.Can recognize that from specification sheets various improvement of the present invention and key element wherein change, equivalent, or improved combination can be undertaken by those technician in this area, and remain as the scope of the invention that in claims, defines in.

Claims (14)

1. the method for production self-supporting activation carbon structure body, this method comprises the following steps:

A) mix the granular activated charcoal, binder material, carbonization reagent and liquid are to prepare semi-plastic mixture, and wherein this binder material comprises the cereal grain of grinding, grain powder or stem tuber powder, this carbonization reagent does not comprise zinc chloride;

B) by use greater than or 100 pounds/square inch compaction pressure come this mixture of compacting to form three-dimensional structure; With

C) in non-oxidizing atmosphere, this structure is heated to greater than or 300 ℃ high temperature, production self-supporting activation carbon structure body.

2. the method for claim 1 comprises that further step d) activates the carbon structure body with self-supporting and is cooled to and is lower than 300 ℃ temperature in non-oxidizing atmosphere.

3. the method for claim 1 is included in after the compacting and dry this structure before heating.

4. the process of claim 1 wherein that this activation charcoal has is lower than No.4 U.S. sieve series mesh size and greater than the granularity of No.325 U.S. sieve series mesh size.

5. the process of claim 1 wherein that this granular activated charcoal is a pellet or fibrous.

6. the process of claim 1 wherein carbonization reagent solvation in this liquid, mix with this granular activated charcoal and this binder material afterwards.

7. the process of claim 1 wherein that this cereal grain is to be selected from wheat, corn, rye, oat, rice, barley and their mixture.

8. the process of claim 1 wherein that this grain powder is a wheat-flour.

9. the process of claim 1 wherein that stem tuber powder is a potato powder.

10. the process of claim 1 wherein that the semi plastic mixture of step a) has uniform denseness.

11. the process of claim 1 wherein that this liquid is water.

12. the process of claim 1 wherein that this carbonization reagent is selected from ammonium chloride, Secondary ammonium phosphate, ammonium iodide, brometo de amonio, ammonium sulfate, primary ammonium phosphate, sulfuric acid and phosphoric acid and their mixture.

13. the process of claim 1 wherein that step a) contains five parts activation charcoal, for this binder material of every 2-5 part.

14. the process of claim 1 wherein that step a) contains certain amount of fluid, this amount is enough to wetting this activation charcoal and this binder material.